JP3060091B2 - Overcoat composition for optical disc - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an overcoat composition for an optical disc. More specifically, a cationic photocurable overcoat containing a propenyl ether terminal group compound that cures rapidly by irradiation with light such as ultraviolet light and forms a cured coating film with excellent adhesion to recording media, hardness, and durability. Composition.

[0002]

2. Description of the Related Art Conventionally, an overcoat agent has been applied to a recording film of an optical disc such as a compact disc recording medium. As the overcoating agent, a radical photocurable overcoating agent such as unsaturated polyester, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate (for example, JP-A-63-96036) is known. Have been. However, photo-radical polymerization-type curing generally causes volume shrinkage, and the adhesion to the recording medium surface tends to decrease.Furthermore, the acrylic composition has a peculiar odor, which causes contamination of the working environment and skin irritation. There is a problem that it is expensive. further,
The presence of air (oxygen) during the UV curing hinders the radical curing reaction, so that it is necessary to perform UV irradiation in an inert gas atmosphere, which also imposes restrictions on the apparatus. In order to improve the problem of such radical curing type,
Although there is an epoxy-based cationic photocurable resin, the resin requires a large amount of UV energy during curing due to low photoreactivity. Therefore, there are drawbacks that a high UV energy irradiation device is required and irradiation time is long. As a method of improving the low reactivity of such a photocationic curable resin, a method of using an alicyclic epoxy compound as a base resin or a diluent has been proposed (Japanese Patent Application Laid-Open No. Hei 5-186755).

[0003]

However, the reaction rate of the photo-cation-curing type using the alicyclic epoxy compound is slower than that of the conventional photo-radical curable resin, and moreover, the alicyclic type is commercially available. The types of epoxy compounds are limited, and it has been difficult to obtain epoxy compounds satisfying practical performance. The present invention relates to an organic solvent, an irritating monomer,
Provided is an overcoat composition for an optical disc that does not contain an oligomer or the like, cures at high speed by irradiating active energy rays such as UV, and gives a cured product having excellent adhesion to a disc substrate, durability, and hardness. The purpose is to: The overcoat composition of the present invention has various problems in the prior art, i.e., harm to workers,
It greatly improves environmental pollution, odor problems, curing speed, coating film properties, and the like.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on an optical disk overcoat agent which solves the above-mentioned problems, and as a result, have reached the present invention. That is, the overcoat composition for an optical disc according to the present invention is characterized by a (poly) ether oligomer having a propenyl ether terminal group represented by the general formula (1), a polyester oligomer having a propenyl ether terminal group, and having a propenyl ether terminal group. It has at least two propenyl ether terminal groups in a molecule selected from the group consisting of urethane oligomers and monomers having propenyl ether terminal groups represented by the general formula (6), (6 ′) or (7). One or more compounds (A) and the cationic photopolymerization initiator (B) are essential components.

[0005]

X ¹ [—O— (AO) m—R ¹ ] n (1) In the formula, n is an integer of 3 to 200;
An integer of 200, and at least one of m is 1 or more. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group,
When m is 2 or more, A may be the same or different,
The (AO) m portion may be random addition or block addition. X ¹ is a polyhydric alcohol residue. ｝

X ¹ [—OR ¹ ] n (6) wherein n is an integer of 2 to 200, and X ¹ is a residue of polyglycerin (2 to 18-mer of glycerin). is there.
At least two of the n R ¹ are propenyl groups, and the rest may be alkyl, acyl or aryl groups. ｝

X ¹ [—O—R ¹ ] n (6 ′) wherein n is an integer of 2 to 200, and X ¹ is a residue of a 2- to 3-trimer of trimethylolalkane. . n R
^At least two of 1 are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

Embedded image Y ¹ [—CO—X ² O—R ¹ ] n (7) ‖ In the formula, n is an integer of 2 to 200, and X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, Y ¹ is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As (A) of the present invention, a urethane oligomer having a propenyl ether terminal group is particularly preferred.

In the general formula (1), A represents a group having 1 to 1 carbon atoms.
12 alkylene, arylene, aralkylene and divalent groups selected from the group consisting of cycloalkylene groups, examples of alkylene groups that can be used include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, Octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include:
Benzylene, 1-phenylene, 2-phenylene, 3
-Phenylpropylene, 2-phenylpropylene, 1-
Phenylpropylene and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene,
Cycloheptylene, cyclooctylene and the like can be mentioned.
Of these, an ethylene group and a propylene group are preferred. If the alkylene group has more than 12 carbon atoms, the solubility of the cationic photopolymerization initiator (B) described later will be poor.

X ¹ is a polyhydric alcohol residue. Examples of the polyhydric alcohol include glycerin, polyglycerin (2 to 18-mer of glycerin, such as diglycerin, triglycerin, tetraglycerin, etc.) and glycidol ring opening. Polymers (compounds having a degree of polymerization of 2 to 5000), trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane and the like) and their dimers and trimers, monopentaerythritol, dipentaerythritol, 3,5-pentaerythritol, sorbitol, sorbitan sorbitan glycerin condensate, and the like. Of these, particularly preferred are glycerin, polyglycerin, and trimethylolalkane and its dimers and trimers.

In the general formula (1), n m is usually an integer of 0 to 200, and at least one of m is usually 1
The above is preferably an integer of 1 to 80, particularly preferably 1 to 5. When m exceeds 200, the viscosity increases (B).
Becomes difficult to dissolve.

N is usually 2 to 200, preferably 3
To 100, particularly preferably an integer of 3 to 5. n is 2
If it exceeds 00, the viscosity increases and the dissolution of the initiator (B) becomes difficult. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.

The polyester oligomer having a propenyl ether terminal group in the present invention includes a compound represented by the following general formula (2), (3) or (4).

[0012] In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by an alkylene diol, arylene diol,
Polyether diol, a residue of any of the diols of the polyurethane diols or polycarbonate diols, Y ¹ is a polyvalent carboxylic acid residue, Y ² is a divalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ² in the general formula (2) is HOX ² O
H is a residue of any of diols of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol.

Specific examples of the alkylene diol represented by HOX ² OH include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonane. Diol, neopentyl glycol, 1.4-cyclohexanediol and the like. Of these, ethylene glycol and propylene glycol are preferred.

Specific examples of arylene diols represented by HOX ² OH include catechol, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
Examples include methane and bisphenol A. Of these, bisphenol A is preferred.

Specific examples of the polyether diol represented by HOX ² OH include poly (oxyethylene) diol, poly (oxypropylene) diol, poly (oxytetramethylene) diol, ethylene oxide adduct of bisphenol A, bisphenol And propylene oxide adduct of A. Of these, poly (oxyethylene) diol and poly (oxypropylene) diol are preferred.

The degree of polymerization of the above polyether diol is usually from 1 to 200, preferably from 2 to 100, particularly preferably from 3 to 3.
-20.

Examples of the polyurethane diol represented by HOX ² OH include reaction products of the following (i) and (ii). (I) H (OX ⁵⁾ diol represented by m-OH (provided that, m is an integer of 1 to 200, X ⁵ is a carbon number 2 to 1
And 2 divalent groups selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups. ) (Ii) a diisocyanate represented by OCN-Z ³ -NCO (However, Z ³ is a divalent group selected from the group consisting alkylene, arylene, a group aralkylene and cycloalkylene.)

In the above diol (i), m is an integer of usually 1 to 200, preferably 3 to 20.

In the diol of the above (i), X ⁵ is 2 selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene groups having 2 to 12 carbon atoms.
Examples of the alkylene group that is a valent group and may be used include methylene, ethylene, propylene, butylene, pentylene,
Hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, particularly preferred are an ethylene group and a propylene group. When the carbon number of the alkylene group is 12
If the ratio exceeds the above range, the solubility of the polymerization initiator (B) becomes poor.

Examples of the diisocyanate (ii) include toluene diisocyanate (TDI), p- and m-phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2 4,4-trimethylhexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4 '-Diphenylmethane diisocyanate,
1,5-tetrahydronaphthalene diisocyanate, naphthalene-1,5'-diisocyanate, bis (2-methyl-3-isocyanatophenyl) methane, 4,4'-
Examples include diphenylpropane diisocyanate, tetramethylxylene diisocyanate (TMXDI), and isophorone diisocyanate (IPDI). Preferred of these are TDI, MDI, IPDI, TDI
MXDI, hydrogenated MDI and HDI.

Examples of the polycarbonate diol represented by HOX ² OH include compounds represented by the following general formula. (However, m is an integer of 1 to 200, and X ⁶ is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene having 2 to 12 carbon atoms.)

M in the above general formula is usually from 1 to 200,
Preferably it is an integer of 3 to 20.

X ⁶ in the above general formula has 2 to 12 carbon atoms.
Alkylene, arylene, aralkylene and a divalent group selected from the group consisting of cycloalkylene, examples of alkylene groups that can be used include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, Octylene, nonylene, decylene, undecylene, dodecylene and the like can be mentioned. Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like. Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, an ethylene group and a propylene group are preferred.

X ³ in the general formula (2) is:
The same as those exemplified as X ^{2 in the} formula (2) can be mentioned, and X ² and X ³ may be the same or different.

In the general formula (2), Y ¹ is a divalent or higher polyvalent carboxylic acid residue, and Y ² is a divalent carboxylic acid residue. Examples of the dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid,
Glutaric acid, adipic acid and the like can be mentioned. Examples of the trivalent or higher polycarboxylic acid include trimellitic acid and pyrimellitic acid. Among them, both Y ¹ and Y ² are preferably at least one member selected from isophthalic acid, terephthalic acid and adipic acid.

In the general formula (2), m is usually from 1 to 20.
It is an integer of 0, preferably 1 to 80, particularly preferably 1 to 20. If m exceeds 200, the viscosity becomes high and the dissolution of the polymerization initiator (B) becomes difficult.

In the general formula (2), n is usually 2 to 20.
It is an integer of 0, preferably 3 to 100, particularly preferably 3 to 20. When n exceeds 200, the viscosity becomes high and the dissolution of the initiator (B) becomes difficult. Further, at least two of the n R ¹ groups are a propenyl group, and the rest are hydrogen atoms,
It may be an alkyl, acyl or aryl group.

Next, the polyester oligomer represented by the following general formula (3) will be described. 中 wherein, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or an arylene group,
X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ¹ in the general formula (3) is the same as that represented by the general formula (1).
X ² , m and n are the same as those represented by the general formula (2).

Next, the polyester oligomer represented by the following general formula (4) will be described. In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are an alkylene diol, an arylene diol, a polyether diol, a polyurethane represented by HOX ² OH and HOX ³ OH, respectively. X ¹ is a residue of a diol of either diol or polycarbonate diol, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

X ¹ in the general formula (4) is the same as that represented by the general formula (1).
X ² , X ³ , m and n are the same as those represented by the general formula (2). X ² and X ³ may be the same or different.

The urethane oligomer having a propenyl ether terminal group in (A) in the present invention is a compound represented by the following general formula (5). {Wherein, m is 0 to 200, n is an integer of 2 to 200, Q ¹ is -OX ² O-or ^{-N (R 2) -X 4 -N} (R
² )-and Q ² is a group represented by -OX ² O-. X ² is an alkyl diol, aryl diol, polyether diol represented by HOX ² OH,
It is a residue of a diol of either polyester diol or polycarbonate diol. -N (R ²⁾ -X ⁴
—N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is alkylene, arylene, aralkylene or cycloalkyl having 2 to 12 carbon atoms. An alkylene group, and R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms. Z
¹ is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (5), ² in Z 2
Examples of the multivalent isocyanate include the same ones as those described in the above formula (ii). As the polyvalent isocyanate for Z ^1, in addition to the above-mentioned divalent isocyanate, lysine ester triisocyanate, modified isocyanate (isocyanurate trimer, buret trimer,
Trimethylolpropane adduct), triphenylmethane triisocyanate, polyphenylmethane polyisocyanate and the like.

In the general formula (5), Q ¹ is —OX ² O—
Or ^{-N (R 2) -X 4 -N} (R 2) - in a group represented, Q ² is a group represented by -OX ² O-. X ² is H
Alkylene diol represented by OX ² OH, ant - diol, polyether diol, a residue of any of the diol polyester diols or polycarbonate diols, X ² is the same as X ² in the general formula (2) Things.

When the HOX ² OH is a polyester diol, the following reaction products of (iii) and (iv) can be mentioned. (Iii) a diol represented by H (OX ⁷ ) m-OH (where m is an integer of 1 to 200, and X ⁷ is a carbon number of 2 to 12)
Is a divalent group selected from the group consisting of alkylene, arylene, aralkylene, and cycloalkylene groups. (Iv) dicarboxylic acid represented by HOOC-Y ³ —COOH (wherein Y ³ is selected from the group consisting of alkylene, arylene, aralkylene and cycloalkylene)
Is a valence group. )

In the diol (iii), m is an integer of usually 1 to 200, preferably 3 to 20.

In the diol of the above (iii), X ⁷
Is a divalent group selected from the group consisting of alkylene having 2 to 12 carbon atoms, arylene, aralkylene and cycloalkylene, and examples of the alkylene group that can be used include:
Methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene,
Decylene, undecylene, dodecylene and the like can be mentioned.
Examples of the arylene group include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Examples of aralkylene include benzylene, 1-phenylene, 2-phenylene, 3-phenylpropylene, 2-phenylpropylene, 1-phenylpropylene, and the like.
Examples of cycloalkylene groups include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene and the like. Of these, an ethylene group and a propylene group are preferred. The alkylene group has 1 carbon atom
If it exceeds 2, the solubility of the polymerization initiator (B) becomes poor.

Examples of the dicarboxylic acid (iv) include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, polycarboxylic acid and the like. Preferred among these are isophthalic acid, terephthalic acid and adipic acid. X ⁴ is the same as X ² in the general formula (2), R ² is the same as A shown in the general formula (1), and m and n are The same as those represented by the general formula (2) can be mentioned.

The monomer having a propenyl ether terminal group in (A) of the present invention is a compound represented by the following general formula (6) or (7). X ¹ [—O—R ¹ ] n (6) In the formula, n is an integer of 2 to 200, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝

In the general formula (6), n is usually 2 to 2
00, preferably an integer of 2 to 6. If n exceeds 200, the viscosity is high and the handling becomes poor. X ¹ is the same as that shown in the general formula (1).

[0042] In the formula, n is an integer of 2 to 200, X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, and Y ¹ Is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups.に お い て In the general formula (7), n is an integer of usually 2 to 200, preferably 2 to 6. If n exceeds 200, the viscosity is high and the handling becomes poor. Y ¹ and X ² are the same as those represented by the general formula (2).

As the cationic photopolymerization initiator (B) used in the present invention, known cationic photopolymerization initiators can be used. Specific examples of (B) include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio)
Phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4-diphenyl-sulfonio) phenyl Sulfide-bis-hexafluorophosphate, bis [4-diphenyl-sulfonio) phenyl] sulfide-bis-hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate and the like. These are readily available from the market. Examples of commercially available products include “SP-150” and “SP-150” manufactured by Asahi Denka Co., Ltd.
170 ";" Irgacure 26 "manufactured by Ciba Geigy
"UVR-697" manufactured by Union Carbide
4 "," UVR-6990 "and the like.

In the present invention, a reactive diluent (C) can be used if necessary for the purpose of adjusting the viscosity of the composition.

As the compound (C), a compound represented by the following general formula (8) can be mentioned. CH ₃ —CH ＝ CH—O—X ² —O—R ³ (8) wherein X ² is an alkylene diol, arylene diol, polyether diol, polyurethane diol or polycarbonate diol represented by HOX ² OH R ³ is a residue of any diol, and R ³ has 2 to 2 carbon atoms.
It is a 12 alkyl, aryl, aralkyl or cycloalkyl group, or a hydrogen atom. ｝

X ² in the above general formula (8) is the same as that represented by the above general formula (2).
³ is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms, or a hydrogen atom.

In the present invention, the weight ratio of (A) :( B) is usually (95-99.9) :( 0.01-
5), preferably (96-98): (2-4).
If the ratio of (B) is less than 0.05, a sufficient effect of initiating polymerization cannot be obtained, and if it exceeds 5, the effect of further improving the curing speed is uneconomical.

When the reactive diluent (C) is used, the amount of (C) is usually 5 to 60% by weight, preferably 10 to 30% by weight, based on the total weight of (A) and (B). %. If the amount of (C) exceeds 60% by weight, the curing speed will decrease.

If necessary, the composition of the present invention may contain a known photo-radical polymerizable composition (D).
The amount of (D) is per 100 parts by weight of the composition of the present invention,
It is usually 0 to 100 parts by weight, preferably 0 to 40 parts by weight.

The composition of the present invention may further comprise, if necessary,
Known epoxy resins (bisphenol A epoxy resin, bisphenol F epoxy resin, tetrabromobisphenol A epoxy resin, novolak epoxy resin, etc.), coloring agents, fillers, non-reactive resins, leveling agents, antistatic agents, solvents And various other additives.

The optical cation-curable overcoat agent for an optical disk comprising the composition of the present invention is applied onto a recording film of an optical disk, and then is cured at high speed by irradiating light energy such as UV, thereby obtaining adhesion and durability. Forms a film with excellent properties. In addition, unlike the conventional photo-radical curing type, the photocuring does not suffer from curing inhibition due to oxygen in the air, and furthermore, there is almost no shrinkage at the time of curing, so that warpage at the time of coating is extremely small.

The method of coating on the optical disk recording film is not particularly limited, and a known method (such as a spin coater)
Can be used. Examples of light that can be used include UV emitted from a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, and the like.

[0053]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. The numerical values in the composition column are parts by weight.

Examples 1 to 6 and Comparative Examples 1 to 3 The overcoat agents prepared according to the formulations shown in Table 1 were
The coating was applied by a spin coater onto an optical disk having a recording film provided on a polycarbonate substrate by sputtering, and the photoreactivity and moisture resistance of the cured film were evaluated according to the following evaluation methods and evaluation criteria. Table 1 shows the obtained evaluation results. Photoreactivity: UV on high pressure mercury lamp on overcoat coated surface
Was irradiated in a predetermined amount, and the curability was observed. The curability was evaluated by rubbing the coated surface with a cotton swab after irradiation with a certain amount of UV, and the degree of adhesion of the uncured material to cotton. Moisture resistance: An optical disk having a cured film obtained by irradiating UV light at 900 mJ / cm ² was left in an atmosphere of 70 ° C. and 90% RH for 1000 hours to evaluate whether or not the cured film was abnormal.

[0055]

[Table 1]

The compounds used in the formulations shown in Table 1 are as follows. The CH ₃ —CH ＝ CH— group (propenyl group) is abbreviated as Pr. Propenyl ether end groups Compound (1): Pr-O- ( CH 2 CH 2 O) 12 -Pr propenyl ether end groups of compound (2): (Y: Terephthalic acid residue) Propenyl ether terminal group compound (3): (X: triethylene glycol residue) (Z: 4,4'-diphenylmethane diisocyanate residue) Propenyl ether terminal group compound (4): (X: triethylene glycol residue) Propenyl ether terminal group compound (5): R [O- (CH ₂ CH ₂ O) ₁₂ -Pr] ₃ (R: glycerin residue) propenyl ether terminal group compound (6): (X ¹ : triethylene glycerin residue) (Y: terephthalic acid residue) (X ² : polyurethane diol residue of the following formula) (Z: 4,4′-diphenylmethane diisocyanate residue) Acrylate terminal compound (7): Epoxy terminal compound (8): "Epicoat 828"
(Bisphenol type epoxy resin manufactured by Yuka Shell Co., Ltd.) Alicyclic epoxy terminal group compound (9): "ERL-422
1 "(manufactured by Union Carbide Corporation, alicyclic epoxy resins) reactive diluent (10): Pr-O- CH 2 CH 2 -OH reactive diluent (11): 2-hydroxyethyl acrylate reactive diluent ( 12): "BRL-4206" (manufactured by Union Carbide Co., Ltd., alicyclic epoxy resin diluent) Photocationic polymerization catalyst (13): "UVR-6974"
<< 50% ethylene carbonate solution of a mixture of p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate and bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, manufactured by Union Carbide Co., Ltd. (14): “Irgacure 18
4 "(made by Ciba-Geigy)

[0057]

The photocationically curable overcoat composition for optical discs containing the compound having a propenyl ether terminal group of the present invention has better curability than conventional radical polymerizable acrylate-based ones, and can be used with a disc substrate. To form a cured coating film having excellent adhesion and moisture resistance. Also,
Higher-speed curability than that of a conventionally known epoxy-based UV cation-curable resin. Due to the above effects, the cationic photocurable composition of the present invention is extremely useful as an overcoat agent for protecting a recording film of an optical disk.

────────────────────────────────────────────────── (5) References US Pat. No. 5,334,772 (US, A) “J. Macromol. Sci., Pure Appl. Chem.”, 1994, A31 (12), p. 1927-1941 (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 4/00 C08F 299/06 C09D 167/07 C09D 175/16 G11B 7/24 CA (STN) CAOLD (STN) REGISTRY (STN )

Claims (8)

(57) [Claims] 1. A (poly) ether oligomer having a propenyl ether terminal group, a polyester oligomer having a propenyl ether terminal group, a urethane oligomer having a propenyl ether terminal group represented by the general formula (1), and a compound represented by the general formula (6): At least one compound (A) having at least two propenyl ether terminal groups in a molecule selected from the group of monomers having a propenyl ether terminal group represented by the general formula (6 ′) or (7), An overcoat composition for an optical disk, comprising a cationic photopolymerization initiator (B) as an essential component. X ¹ [—O— (AO) m—R ¹ ] n (1) In the formula, n is an integer of 3 to 200, and n m is 0 to
An integer of 200, and at least one of m is 1 or more. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. A is an alkylene having 2 to 12 carbon atoms, arylene, aralkylene or cycloalkylene group,
When m is 2 or more, A may be the same or different,
The (AO) m portion may be random addition or block addition. X ¹ is a polyhydric alcohol residue. X ¹ [—OR ¹ ] n (6) wherein n is an integer of 2 to 200, and X ¹ is a residue of polyglycerin (2 to 18 mer of glycerin) It is.
At least two of the n R ¹ are propenyl groups, and the rest may be alkyl, acyl or aryl groups. X ¹ [—O—R ¹ ] n (6 ′) wherein n is an integer of 2 to 200, and X ¹ is a residue of a trimer of trimethylolalkane. is there. n R
^At least two of 1 are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image Y ¹ [—CO—X ² O—R ¹ ] n (7) ‖ In the formula, n is an integer of 2 to 200, and X ² is a residue of any one of alkylene diol, arylene diol, polyether diol, polyurethane diol and polycarbonate diol represented by HOX ² OH, Y ¹ is a polyvalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 2. A polyester oligomer having a propenyl ether terminal group is represented by the following general formula (2) or (3):
Alternatively, the composition according to claim 1, wherein the general formula is an oligomer represented by formula (4). Embedded image Y ¹ [—CO— (X ² O—CY ² C—O) m—X ³ O—R ¹ ] n (2) ‖ ‖ ‖ O O O ｛In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are HOX ² OH and HOX ³ OH, respectively.
Represented by an alkylene diol, arylene diol,
Polyether diol, a residue of any of the diols of the polyurethane diols or polycarbonate diols, Y ¹ is a polyvalent carboxylic acid residue, Y ² is a divalent carboxylic acid residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image X ¹ [—O— (CX ² O) m—R ¹ ] n (3) ‖ In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, X ² is an alkylene or an arylene group,
X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ Embedded image X ¹ [-(OX ² OC) m-OX ³ O-R ¹ ] n (4) ‖ In the formula, m is an integer of 1 to 200, n is an integer of 2 to 200, and X ² and X ³ are respectively HOX ² OH, alkylene diol represented by HOX ³ OH, arylene diol, polyether diol, X ¹ is a residue of a diol of either polyurethane diol or polycarbonate diol, and X ¹ is a polyhydric alcohol residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 3. The composition according to claim 1, wherein the urethane oligomer having a propenyl ether terminal group is an oligomer represented by the following general formula (5). Embedded image Z ¹ [-NC- (Q ¹ -C-NZ ² NC) m-Q ² -R ¹ ] n (5) ｜ ‖ ｜ ｜ ｜ ‖ H O O H During H O {wherein, m is 0 to 200, n is an integer of 2 to 200, Q ¹ is -OX ² O-or ^{-N (R 2) -X 4 -N} (R
² )-and Q ² is a group represented by -OX ² O-. X ² is a residue of any one of alkyl diol, aryl diol, polyether diol, polyester diol and polycarbonate diol represented by HOX ² OH. -N (R ²⁾ -X ⁴ -
N (R ² ) — is a diamine residue represented by HN (R ² ) —X ⁴ —N (R ² ) H, and X ⁴ is an alkylene, arylene, aralkylene or cycloalkylene group having 2 to 12 carbon atoms. R ² is an alkyl, aryl, aralkyl or cycloalkyl group having 2 to 12 carbon atoms Z ¹ is a polyvalent isocyanate residue, and Z ² is a divalent isocyanate residue. At least two of the n R ¹ groups are propenyl groups, and the rest may be hydrogen atoms, alkyl, acyl or aryl groups. ｝ 4. The weight ratio of (A) :( B) is (95-9)
9.9): The composition according to any one of claims 1 to 3, which is (0.01 to 5). 5. The method according to claim 1, further comprising a reactive diluent (C), wherein the content of (C) is 5 to 60% by weight based on the total weight of (A) and (B). 5. The composition according to any of 4. 6. The composition according to claim 5, wherein (C) is a reactive diluent represented by the following general formula (8). CH ₃ —CH ＝ CH—O—X ² —O—R ³ (8) wherein X ² is an alkylene diol, arylene diol, polyether diol, or polyurethane diol represented by HOX ² OH Or a residue of any diol of polycarbonate diol, wherein R ³ has 2 to 2 carbon atoms.
12 alkyl, aryl, aralkyl, cycloalkyl groups or hydrogen atoms. ｝ 7. An overcoat composition for an optical disk, wherein the composition according to claim 1 further comprises an epoxy resin. 8. An optical disk obtained by applying and curing the composition according to claim 1 on a recording coating film.